{[Cp*Ru(CO)2]2(μ-H)}(+)OTf(-) | 198824-38-3

• 英文名称: {[Cp*Ru(CO)2]2(μ-H)}(+)OTf(-)
• 英文别名: bis(dicarbonyl)(μ-hydrido)(pentamethylcyclopentadiene)ruthenium trifluoromethanesulfonate；[(η5-C5Me5Ru(CO)2)2(μ-H)]OSO2CF3；[(η(5)-C5Me5)2Ru2(CO)4](+)CF3SO3(-)；[((C5(CH3)5)Ru(CO)2)2(μ-H)](triflate)
• CAS: 198824-38-3
• 化学式: CF₃O₃S*C₂₄H₃₁O₄Ru₂
• 分子量: 734.718
• InChiKey: LYWXOMVGRBXZQV-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  [η(5)-Me5C5Ru(CO)2]2 、 三氟甲磺酸 以 二氯甲烷 为溶剂， 生成 {[Cp*Ru(CO)2]2(μ-H)}(+)OTf(-)
  参考文献：
  名称：

  环戊二烯基配体对Cp'（2）Ru（2）（CO）（4）配合物中Ru-Ru键的质子化焓的影响。

  摘要：

  一系列Cp'（2）Ru（2）（CO）（4）配合物的碱性是通过测量CF（3）SO（3）H质子化配合物时产生的热量（DeltaH（MHM））来确定的。 1,2-二氯乙烷在25.0摄氏度下进行。光谱研究表明，质子化发生在金属-金属键上，形成[Cp'（2）Ru（2）（CO）（4）（＆mgr; -H）]（+ ）CF（3）SO（3）（-），其中所有CO配体都为末端。Cp'（2）配体的碱度（-DeltaH（MHM））按以下顺序增加：（C（5）Me（4）CF（3））（2）<（C（9）H（7） ）（2）

  DOI：

  10.1021/ic970181e
• 作为试剂：
  描述：

  苯基乙二醇 在 {[Cp*Ru(CO)2]2(μ-H)}(+)OTf(-) 、 三氟甲磺酸 、 氢气 作用下， 以 环丁砜 为溶剂， 110.0 ℃ 、5.17 MPa 条件下， 反应 8.0h， 以66%的产率得到苯乙醇
  参考文献：
  名称：

  1,2-丙二醇的催化脱氧给ñ丙醇

  摘要：

  Abstractmagnified imageDeoxygenation of 1,2‐propanediol (1.0 M in sulfolane) catalyzed by bis(dicarbonyl)(μ‐hydrido)(pentamethylcyclopentadiene)ruthenium trifluoromethanesulfonate ({[Cp*Ru(CO)2]2(μ‐H)}+OTf−) (0.5 mol%) at 110 °C under hydrogen (750 psi) in the presence of trifluoromethanesulfonic acid (HOTf) (60 mM) gives n‐propanol as the major product, indicating high selectivity for deoxygenation of the internal hydroxy group over the terminal hydroxy group of the diol. The deoxygenation of 1,2‐propanediol is strongly influenced by the concentration of acid, giving faster rates and proceeding to higher conversions as the concentration of HOTf is increased. Propionaldehyde was observed as an intermediate, being formed through acid‐catalyzed dehydration of 1,2‐propanediol. This aldehyde is hydrogenated to n‐propanol through an ionic pathway involving protonation of the aldehyde, followed by hydride transfer from the neutral hydride, dicarbonyl(pentamethylcyclopentadiene)ruthenium hydride [Cp*Ru(CO)2H]. The proposed mechanism for the deoxygenation/hydrogenation reaction involves formation of a highly acidic dihydrogen complex [Cp*Ru(CO)2(η2‐H2)]+ OTf−.

  DOI：

  10.1002/adsc.200800685

文献信息

• Catalytic Ionic Hydrogenation of Ketones by {[Cp*Ru(CO)₂]₂(μ-H)}⁺
  作者：Paul J. Fagan、Mark H. Voges、R. Morris Bullock

  DOI：10.1021/om901005k

  日期：2010.2.22

  [Cp*Ru(CO)(2)](2)(mu-H)}+OTf- functions as a homogenous catalyst precursor for hydrogenation of ketones to alcohols, with hydrogenations at 1 mol % catalyst loading at 90 degrees C under H-2 (820 psi) proceeding to completion and providing > 90% yields. Hydrogenation of methyl levulinate generates gamma-valerolactone, presumably by ring-closing of the initially formed alcohol with the methyl ester. Experiments in neat Et2C=O show that the catalyst loading can be <0.1 mol% and that at least 1200 turnovers of the catalyst can be obtained. These reactions are proposed to proceed by an ionic hydrogenation pathway, with the highly acidic dihydrogen complex [Cp*Ru(CO)(2)(eta(2)-H-2)](+) OTf- being formed under the reaction conditions from reaction of H-2 with [Cp*Ru(CO)(2)]2(mu-H)](+) OTf-